DE2152826A1 - New N phosphonomethylglycines and phytotoxic compounds containing such compounds see agents - Google Patents

Description

PATENT LAWYERS

DR. O. DlTTMANN KL SCHIFF DR. A. ν. FIVE BR DIPL. ING. P. STHBHL 8 MUNICH Θ0 MARIAHII-FPLATZ 8 & 8

DA-449S

Description of the patent application

of the company

MONSANTO COMPANY

800 North Lindbergh Boulevard

St. Louis, Missouri 63166

UNITED STATES.

concerning

Novel N-phosphonomethylglycines and phytotoxic agents containing such compounds

Priorities: March 10, 1971, USA, No. 123 057 Aug. 9, 1971, USA, No. 170 385

The invention relates to new N-phosphonomethylglycines, which are effective as herbicides or phytotoxic agents. As used herein, the term "phytotoxic gowns" is intended to mean fabrics denote that (1) effectively control all plants in a given location, or (2) the growth of one plant species or selectively control of several plant species in the presence of other plants. Likewise, the The terms "phytotoxic" and "phytotoxicity" are used to to denote the overall and selective control effectiveness of the compounds and agents according to the invention.

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As used herein, the term "control" is intended to follow Punctures include: (1) killing, (2) inhibiting growth, reproduction, or sprouting. Proliferation and (3) the removal, destruction or otherwise reduction of incidence, and the activity of plants.

As used herein, the term "plants" is intended to include land plants and aquatic plants.

The term "land plants" used herein is intended to germinate Seeds, emerging seedlings and the herbaceous vegetation including the roots and the parts above ground include, as well as trained woody plants.

As used herein, the term "aquatic plants" is intended to mean algae and higher aquatic plants. The term "higher aquatic plants" means aquatic plants that are botanically higher stand as algae. This term is intended to include plant organisms growing in the water, a major part of which is normally is largely submerged, e.g. roots, as in Lemna, leaves, as in Vallisneria, or entire plants, as with Anacharis. Thus, the term "higher aquatic plants" is intended to include all aquatic plants, whether or not they are now around plants normally floating freely in the surrounding water, such as Salvinia, or submerged species that normally Rooted in the ground, like Vallisneria, acts, as well as the species, in every way, either free floating, or rooted, like Anacharis or Alternanthera, grow normally.

The invention relates to new phosphonomethylglycines of the general formula

₉ C
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1 2
wherein R, R and R, which can be the same or different, halogen; -OH; -SH;

NR R, where R and R ^, the same or different can be hydrogen, alkyl and hydroxyalkyl with 1 to 4 carbon atoms, alkenyl with 2 to 4 carbon atoms and where R and R ^ together with the nitrogen atom are one can form heterocyclic ring;

-OR ^ and -SR ^, where R ^ monovalent hydrocarbon groups, monovalent hydrocarbonoxy hydrocarbon groups each having 1 to 18 carbon atoms, halogenated monovalent Hydrocarbon groups, halogenated monovalent hydrocarbonoxy hydrocarbon groups each having 1 to 18 carbon atoms and 1 to 3 halogen atoms and / or the groups

-CH _2n -NtT c ι where η is 1 to 4 and R and R ^ have the meanings given above, with the proviso that no more than two of the groups R, R and R ² -NR R ^, -OR ³ or -SR ^ are and

-OR, where R is a salt-forming cation of alkali metals, alkaline earth metals, copper, zinc, manganese, nickel, ammonium and / or organic ammonium, provided that when the organic group is an aryl group, the ammonium salt is a primary amine salt or a mixture of such salts,

1 2 with the proviso that when a substituent of R, R and R

1 is 2 halogen, the other substituents of R, R and R are not -OR, and with the further proviso that not more than

AOf. f.

two of the substituents R, R and R are -OR when R is ammonium or organic ammonium,
mean

as well as the salts of strong acids of such compounds,

1 2
where R, R and R are -OH groups, the strong acids having a pK value of 2.5 or less.

-4-209839 / 1201

As used herein, the term "halogen" is intended to mean chlorine, bromine, iodine and fluorine.

As used herein, the term "monovalent hydrocarbon" is intended to include alkyl, alkenyl, alkynyl, aralkyl of straight-chain and branched radicals such as methyl, ethyl, isopropyl, cyclopropyl, cyclohexyl, tertiary butyl, n-butyl and the various forms of amyl, hexyl, heptyl, octyl, Nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, Hexadecyl, heptadecyl, octadecyl, benzyl, phenylethyl, naphthylethyl, tolylethyl, methylbenzyl, phenylbenzyl, and the corresponding alkenyl and alkynyl groups and the like, aryl groups and alkaryl groups, such as phenyl, tolyl, Xy-IyI, Naphthyl, vinylphenyl, and the like. It is preferred that the monovalent hydrocarbon group 1 to Comprises carbon atoms and that it is an alkyl, alkenyl or alkynyl group.

The monovalent hydrocarbonoxy hydrocarbon groups expressed by the substituent Rr include alkoxyalkyl, alkenoxyalkyl, alkoxyalkoxyalkyl, alkenoxyalkoxyalkyl, dialkoxyalkyl, alkenoxy (alkoxy) alkyl, alkenoxyalkoxy (alkoxy) alkyl, alkoxyalkoxy (alkoxy) alkyl, aryloxyalkyl, such as 2-methoxyarylalkyl and alkoxyarylalkyl , 4-ethoxy-2-methy! Butyl, 2-ethoxyethyl, 3-propoxypropyl, 4-methoxybutyl, * 4- methoxy-2-ethylbutyl, ^ -butoxybutyl, 2-allyloxyethyl, 2-butenoxyethyl, ^ -butenoxybutyl, 2- (2-methoxyethoxy) ethyl, 2- (2-butoxyethoxy) ethyl, ^ -O-methoxypropoxy) butyl, 2- (3-allyloxypropoxy) ethyl, 2- (2-buteneoxyethoxy) ethyl, phenoxyethyl, naphthoxyethyl , Butyl, 2,4-diethoxyphenyl, 2-methoxyphenyl, tolylosyethyl, ^ - phenoxybutyl, trifluoromethylphenyl and the like.

As examples of halogenated monovalent hydrocarbon groups, which are represented by the substituent E ^, can are mentioned haloalkyl, such as chloromethyl, iodomethyl, bromoethyl, fluoromethyl, chloroethyl, iodoethyl, bromoethyl, 1,2-dichloroethyl, 1,2-diiodoethyl, 2,2-dibromoethyl, chlorine-n-propyl,

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Bromo-n-propyl, iodoisopropyl, bromo-n-butyl, bromo-tert-butyl, 1,3,3-trichlorobutyl, 1,3,3-tribromobutyl, chloropentyl, bromopentyl, 2,3-dichloropentyl, 3,3- Dibromopentyl, chlorhexyl, bromhexyl, 2,4 ~ dichlorohexyl, 1,3-dibromohexyl, 1,3,4-trichlorohexyl, chloroheptyl, bromoheptyl, fluoroheptyl, 1,3-dichloroheptyl, 1,4,4-trichloroheptyl, 2,4- Dichloromethylheptyl, chlorooctyl, bromooctyl, iodootyl, 2,4-dichloromethylhexyl, 2,4-dichloroctyl, 2,4,4-trichloromethylpentyl, 1,3,5-tribromooctyl, and halogenated straight-chain and branched radicals of nonyl, decyl, undecyl, dodecyl , Tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, haloalkenyl, such as chlorovinyl, bromovinyl, chlorallyl, bromoallyl, 3-chloro-n-butenyl-1,3-chloropentenyl-1, ^ -chloro-n-hexenyl- 2, 3, ^ - dichloromethylpentenyl-l, 3-fluorine-n-heptenyl-l, 1,3,3-trichloro-n-heptenyl-5, 1,3,5-trichloro-n-octenyl-6, 2, 3,3-Trichloromethylpentenyl- ⁱ f and the various homologues and isomers of haloalkenyl with 2 to 12 carbon atoms, Halog enaryl such as o-chlorophenyl, m-chlorophenyl, m-bromophenyl, p-chlorophenyl, 2, i} -dichlorophenyl, 3,5-dichlorophenyl, 2,5-diiodophenyl, and the like. The halogenated monovalent hydrocarbonoxy hydrocarbon groups represented by R- are alkoxy- and aryloxy-substituted derivatives of the abovementioned halogenated monovalent hydrocarbon groups with the meaning given above for the alkyl and aryl groups.

The term "alkali metal" as used herein includes lithium, Sodium, potassium, cesium and rubidium. The term "alkaline earth metal" includes beryllium, magnesium, calcium, strontium and barium.

The organic ammonium salts of the above formula are prepared from low molecular weight organic amines, i.e. from those which have a molecular weight below about 300. Examples of such organic amines are the alkyl amines, alkylene amines and alkanolamines with no more than two amino groups, such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butyl

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amine, isobutylamine, sec-butylamine, n-amylainine, isoamylamine, Hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, Dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, Methylisopropylamine, methylhexylamine, methylnonylamine, Methylpentadecylamine, methyloctadecylamine, ethylbutylamine, Ethylheptylamine, Ethyloctylamine, Hexylheptylamine, Hexyloctylamine, dimethylamine, diethylamine, di-n-propylamine, Diisopropylamine, di-n-amylamine, diisoamylamine, dihexylamine, Diheptylamine, dioctylamine, triethylamine, triethylamine, trin-propylamine, Triisopropylamine, tri-n-butylamine, triisobutylamine, Tri-sec-butylamine, tri-n-amylamine, ethanolamine, n-propanolamine, Isopropanolamine, diethanolamine, Ν, Ν-diethylethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-diroethylbutenyl-2-amine, Dibutenyl-2-amine, n-hexenyl-2-amine and propylenediamine, primary Arylamines, such as aniline, methoxyaniline, ethoxyaniline, o, m, p-toluidine, Phenylenediamine, 2,4,6-tribromaniline, benzidine, naphthylamine, o, m, p-chloroaniline and the like, heterocyclic amines, such as pyridine, morpholine, piperidine, pyrrolidine, indoline, azepine and the like.

Preferred compounds according to the invention are those

1 2 T where at least one of the substituents B, R and R OR ^ or OR and the remaining substituents R, R and R are OH, SH or OR. More preferred compounds of the invention are those where at least one of the substituents R, R and R are OR and the other R, R and R are OH, and where R is a salt-forming cation. The particularly preferred compounds of this invention are those at

12 6

where one of the substituents R, R and R is OR and the rest OH and in which R is ammonium or an organic ammonium group, the organic ammonium group being monoalkylammonium, Dialkylammonium, trialkylammonium, monoalkenylammonium, Dialkenylammonium, trialkenylammonium, monoalkynylammonium, Dialkinylammonium, Triaikinylammonium, Monoalkanolammonium, Dialkanolammonium, trialkanolammonium, a heterocyclic Is ammonium and / or an arylammonium, and where

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the organic ammonium group contains 1 to 18 carbon atoms.

A compound which is encompassed by the above formula, namely N-phosphonomethylglycine, is already known. These

1 2 connection results when the substituents R, R and R are each -OH.

The remaining compounds of the invention according to the general formula are new. All compounds of the invention are however, new herbicides or phytotoxic agents.

N-phosphonomethylglycine is a very potent phytotoxic Kittel or Herbieid. But because it is in water and in the conventional is relatively insoluble in organic solvents, it is not so well suited for commercial preparations, how many of its derivatives. It is therefore generally preferred to use the more soluble compounds of the invention 2u, in which at least one of the hydrogen atoms in the hydroxyl or thiol groups of N-phosphonomethylglycine through an alkali metal or alkaline earth metal has been replaced or has been combined with ammonia or an organic amine. The aminoalkyl esters of N-phosphonomethylglycine are also used effective phytotoxic agents, surprisingly these and other compounds encompassed by the above general formula are water-soluble, but show the same high activity like glycine.

Furthermore, the N-phosphonomethylglycine can be easily dehydrated, whereby linear and cyclic anhydrides are formed which are also excellent phytotoxic gowns or herbicides.

The N-Phosphonomethylglycine can by phosphonomethylation of glycines, preferably with chloromethylphosphonic acids. You can also use phosphite addition to be prepared on azomethines. For example, the reaction of ethyl glycinate with formaldehyde and diethyl phosphite leads to the tri-

20983B / 1201 ^J * ^F

ethyl ester of N-phosphonomethylglycine. The compounds of the invention can also readily by oxidation of the corresponding aminophosphinated compounds with mercury chloride and other oxidizing agents are obtained «The N-Phosphonomethylglycine are granular or crystalline solids that are generally water soluble.

The strong acids that salts with the N-phosphonomethylglycine are those that have a pK value of 2.5 or ivenigor to have. Examples include hydrochloric acid, sulfuric acid, phosphoric acid, trifluoroacetic acid and trichloroacetic acid and the same. In some cases these salts are isolated as hemisalts, i.e. one molecule of the acid connects with two oils of N-Phosphonornethylglycins. she can also contain water of hydration.

The acid halides of N-phosphonomethylglycine are produced by known methods. For example, the chlorine derivatives can be prepared by reacting N-phosphonomethylglycine with PCIc or SOCl ₂ in an anhydrous solvent medium, such as ether and the like, or another organic solvent «.

The amides, esters and thioesters of N-phosphonomethylglycine can by reacting the acid halide in a solvent with the respective amine, thiol or alcohol in the presence of one Hydrogen halide acceptors such as triethylamine, pyridine and the like can be prepared. Another way is the ester exchange reaction with the methyl ester of N-phosphonomethylglycine.

The salts of N-Phosphonomethylglycins are by partial or complete neutralization of the acid with the respective Base, the basic carbonate, ammonia or the organic amine.

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According to the invention it has been found that the growth of germinating seeds, emerging seedlings, maturing and developed woody and herbaceous vegetation and of aquatic plants can be controlled by the emerging seedlings or the above-ground parts of the ripening and developed vegetation or aquatic plants to the action of an effective amount of the invention Glycine exposed. These connections can be used either alone or as mixtures of two or more compounds or as mixtures with auxiliaries, These compounds are effective as post-exposure phytotoxins or herbicides, ie. they are used to be selective Control of the growth of one or more monocotyledonous species and / or of one or more dicotyledonous species Species suitable in the presence of other monocot and / or dicot species. Further are the connections the invention characterized by a broad spectrum of activity, that is, they are able to control the growth of a wide variety of plants. examples for this are Ferns, gonifera (pine, pine, pine and the like), aquatic, monocot and dicotyledonous plants.

The invention is illustrated in the examples. Unless otherwise stated, all parts and percentages are given therein based on weight.

example 1

A mixture of about 50 parts of glycine, 92 parts of chloromethylphosphonic acid, 150 parts of a 50 # aqueous sodium hydroxide solution and 100 parts of water were added to a suitable reaction vessel introduced and kept at reflux temperatures, while another 50 parts of a 50 # strength aqueous sodium hydroxide solution were added. The pH of the reaction mixture was determined by the rate of addition of the sodium hydroxide held between 10 and 12. After adding all of the alkali

209839/1201 ~ ¹⁰ ~

solution, the reaction mixture was refluxed for a further 20 hours, cooled to room temperature and filtered off. About 160 parts of concentrated hydrochloric acid were then added to this and the mixture was filtered off, whereby a clear solution is obtained from which N-phosphonomethylglycine slowly separated. This material had a melting point of 23O ⁰ C with decomposition.

Calculated for C ₃ HgNO ₅ P: C 21.31, H ^ 77, N 8.28 Found: C 21.02, H 5.02, N 8.05.

Example 2

Using the following method, N-phosphonomethylglycine was also made produced by the oxidation of N-phosphinomethylglycine.

A mixture of about 10? Parts phosphinomethylglycine, 625 Parts of mercury (II) chloride and 50 parts of water were in a suitable reaction vessel was placed in and held at reflux temperature for about two hours. The result of the reaction Mercury (I) chloride precipitated and was filtered off removed. The piltrate was saturated with hydrogen sulfide and the resulting mercury (II) sulfide became separated by filtration. A clear filtrate was thus obtained, which was concentrated under reduced pressure became. The residue was diluted with 10 parts of water. The crystalline precipitate was collected and washed with methanol and then washed with diethyl ether. The product thus obtained was the same as that of the previous example identical.

Example 3

A mixture of about 17 parts of N-phosphonomethylglycine, 100 parts of water and 7 parts of potassium carbonate was in a suitable Reaction vessel stirred at room temperature. Mach complete dissolution, which is achieved by clarifying the reac-

209839/1201

tion mixture indicated, the reaction mixture was up concentrated on a steam bath at reduced pressure. The residue was washed with hot methanol and then with diethyl ether washed. The product thus obtained was the monopotassium salt of N-phosphonomethylglycine hemihydrato

Calculated for C ₃ H ₇ NO ₅ PK ^ aH ₂ O: C 16.65, H 3.70, N 6, kG

Found: G 16.67, H 3.85, N 6.32.

By increasing the amount of potassium carbonate used, the corresponding dipotassium and tripotassium content can be increased. ze des N-PhosphonoiT.ethylglyoins are produced. In practically the same way, the corresponding ammonium salts and the salts of ancloidal alkali metals and of alkaline earth metals as well as copper, zinc, manganese and nickel can be produced.

Koch oi er I'ethode were the following salts of N-Phosphonorc.i.hvj f lycirjr obtained as white powder:

Kono-, di- and trisodium salts, Κόπο-, di- and trilithium salts.

Example ^

About 170 parts of li-phosphonomethylglycine became a solution given by 45 parts of dinethylamine in 10 parts of water was dissolved and contained in a suitable reaction vessel. The reaction mixture cleared up within a short time Period during which the mixture was stirred, 'the resulting Solution was then concentrated by heating to 100 ° C under reduced pressure. When residue was a viscous oil was obtained from which a crystalline solid was obtained. This product was called the monodimethylamine salt of N-phosphonomethylglycine identified ". Mp. 150 ° C below Decomposition.

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⁸ AD ORIGINAL

Calculated for C ₅ H ₁₅ N ₂ O ₅ P: C 28, Oi +, η 7, O6, N 13.08, P 14-, 66

Found: C 27.88, H 6.92, N 12.88, P 14.22

Using the above method, other amine salts of N-phosphonomethylglycine e.g. the pyridine salts (monosalt - white solid), the diethylamine salts, the morpholine salts, the piperidine salts, the ethanolamine salt (flowing powder to a viscous liquid), the annnonium salt (White dust).

Example 5

Gaseous hydrogen chloride was through a suspension of 6 g (0.0355 mol) of N-phosphonomethylglycine in excess Passed methyl alcohol until a clear solution was obtained. The solution was concentrated under reduced pressure and the residue was mixed with a methanol solution, which contained at least one equivalent of triethylamine. The solvent was removed under reduced pressure and the Debris was extracted with ether until it assumed a granular shape. The granular solid eventually became extracted with methanol to remove triethylamine hydrochloride. The insoluble product, methyl N-phosphonomethyl glycinate, was obtained in excellent yield. After recrystallization from dilute methanol, the one obtained melted Product at 208.5 ° C with decomposition.

. Calculated for C 1 H ₁₀ NO ₅ P: C 26.24, H 5.50

Found: C 26.15, H 5.43

The following esters were prepared according to the above procedure (all of them at the specified temperatures below Decomposition melted):

Dodecyl-N-phosphonomethylglycinate 197-200 ⁰ C chloroethyl-N-phosphonomethylglycinate "20? ° C ethyl-N-phosphonomethylglycinate 203 ° C

209839/1201 ~ ¹³ -

¹³ "2T52826

t ■

Cyclohexyl-N-phosphonomethyl glycinate 195 ° C

Decyl N-phosphonomethyl glycinate 201-204 ° C

Hexyl-N-phosphonomethylglycinate 202 ⁰ C

Octyl-N-phosphonomethylglycinate 200 ⁰ C

n-Butyl-N-phosphonomethyl glycinate 207-209 ° C Propyl N-phosphonomethyl glycinate 208.5 ° C

Example 6

A mixture of 10 g (0.055 mol) of methyl N-phosphonomethyl glycinate and excess concentrated aqueous ammonium hydroxide was heated to reflux temperature for two hours. The solution was then concentrated under reduced pressure and the residue obtained was washed with ether and methanol. The granular product thus formed was stirred with a mixture of excess glacial acetic acid in methanol. The precipitated solid was collected, washed with methanol and crystallized from dilute ethanol. The yield of N-phosphonomethylglycine amide, pp. 22 ° C. with decomposition, was 8.0 g or 87% of theory.

Calculated for C ₃ H ₉ N ₂ O ^ P: C 21, Mi-, H 5.40

Found: C 21.26, H 5.39

Example 7

A solution of 16.9 g (0.10 mol) of N-phosphonomethylglycine in 300 ml of hot water was heated to reflux temperature with 5.6 g (0.10 mol) of calcium oxide. After about 10 minutes the mixture was cooled and filtered. The residue was washed with methanol and ether. After air drying, the yield of the calcium salt of N-phosphonomethylglycine hydrate was 17.5 g or 84% of theory.

Calculated for C ₃ H ₆ NO ₅ PCa ^ 1 / 2H ₂ O: C 13.73, H 4.05, Ca 15.76

Found: C 13.75, H 4.20, Ca 15.28

« 14-209 8 39/1201

Example 8

-A mixture of 17 g (0.10 mol) of N-phosphonomethylglycine and 2 g (0.05 mol) of magnesium oxide in 300 ml of water was heated to reflux temperature for 10 minutes. The solution was on Chilled to room temperature and filtered to remove a small amount of sediment. The clear piltrate then became concentrated at reduced pressure and the granular The residue was washed with methanol and ether. In this way, magnesium bis-N-phosphonomethylglycinate hydrate became obtained in excellent yield.

Calculated for C ₆ H ₁ → N ₂ O ₁₀ P ₂ Mg * 2 1 / 2H ₂ O: C 17.79, H 4.57, Mg 5.5

Found: C 17.80, H 4.69, Mg 6.0

Example 9

A mixture of 20 grams (0.11 moles) of methyl N-phosphonomethyl glycinate and about 23 grams (0.33 moles) of pyrrolidine was heated on a steam bath for two hours. Excess amine was then removed under reduced pressure and the residue was washed with ether and tetrahydrofuran. The gummy product was stirred with a mixture of excess glacial acetic acid in methanol and the crystalline precipitate was collected by filtration. After washing with methanol and ether, the tetramethylene-N-phosphonomethylglycine amide, boiling point 243 ° C. with decomposition, was obtained in a yield of 12 g or k9% of theory. The product was recrystallized from dilute ethanol for analysis.

Calculated for C ₇ H ₁₅ N ₂ O ^ P: C 37.84, H 6.81

Found: C 37.82, H 6.96

Example 10

N-Phosphonomethylgfycin (lo g) was placed in a small beaker and covered with concentrated hydrochloric acid (approximately 5 ml).

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After the exothermic reaction subsided, the mixture was allowed to stand for about 10 to 15 minutes. The crystalline solid was washed with tetrahydrofuran and then in air dried, producing the N-phosphonomethylglycine hemihydrochloride hemihydrate (Melting point above 300 ° C.) was obtained with practically quantitative yield.

Other compounds of the invention can be prepared using the procedures described above, as follows Fabrics include:

N-chlorophosphonylmethylglycine

N-dichlorophosphonylmethylglyc in

N-phosphonomethyl glycinyl chloride N-phosphonomethylglycinyl bromide

N-phosphonomethylglycinyl iodide

N-phosphonomethyl glycinyl fluoride N-dichlorophosphonylmethylglycinyl chloride N-Dibromophosphonyl methyl glyc in

N-Di, iodophosphonylmethylglycine

Monopyridine salt of N-phosphonomethylglycine Monobutylamine salt of N-phosphonomethylglycine Mono- (trimethylamine) salt of N-phosphonomethylglycine Konopyrrolidinsalz des N-Phosphonomethylglycins Mono- (diethylenetriamine) -salz of N-Phosphonomethylglycins Monoisopropylamine salt of N-phosphonomethylglycine, mono-n-propylamine salt of N-phosphonomethylglycine, Monomorpholine salt of N-phosphonomethylglycine Mono- (dipropargylamine) salt of N-phosphonomethylglycine Monosodium salt of ethyl N-phosphonomethylglycinate Potassium salt of ethyl N-phosphonomethylglycinate Mono- (dialkylamine) salt of N-phosphonomethylglycine Monolithium salt of ethyl-N-phosphonomethylglycinate Propyl N-phosphonomethyl glycinate monosodium salt Conosodium salt of methyl N-phosphonomethyl glycinate Monosodium salt of chloroethy1-N-phosphonomethylglycinate Monosodium salt of hexyl-N-phosphonomethylglycinate

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Monopotassium salt of methyl-N-phosphonomethylglyclnate Monopotassium salt of propyl-N-phosphonomethylglycinate Monopotassium salt of butyl-N-phosphonomethylglycinate Monopotassium salt of hexyl-N-phosphonomethylglycinate Monopotassium salt of chloroethyl-N-phosphonomethylglycinate Mono (picoline) salt of N-phosphonomethylglyein Monocyclohexylamine salt of N-phosphonomethylglycine. Di (methylamine) salt of N-phosphonomethylglycine Di- (dimethylamine) salt of N-phosphonomethylglycine Di- (- ethylamine) salt of N-phosphonomethylglycine Di (n-propylamine) salt of N-phosphonomethylglycine Di- (isopropylamine) salt of N-phosphonomethylglycine Di (morpholine) salt of N-phosphonomethylglycine Mono- (oleylamine) salt of N-phosphonomethylglycine Mono- (stearylamine) salt of N-phosphonomethylglycine Mono (tallowamine) salt of N-phosphonomethylglycine Mono- (methylbutylamine) salt of N-phosphonomethylglycine N-difluorophosphonylmethylglycine

N-phosphonomethylglycine hemihydrobromide hemihydrate N-phosphonomethylglycine
N-thiolphosphonomethylglycine
N-dithiolphosphonomethylglycine
Chloropropyl-N-phosphonomethylglycine N-trithiolphosphonomethylglycine
Phenyl-N-phosphonomethylglycinate naphthyl-N-phosphonomethylglycinate methoxyethyl-N-phosphonomethylglycinate dimethyl-N- (phosphonomethyl) -glycinate Jfethyl-N-phosphonomethylthiolglycine decyl-N-phosphonomethylthiolglycine octadecyl-N-phosphonomethyl-thiol-glycine), N-phosphonomethyl-thiol-glycine), N-phosphonomethyl-thiolglycine), N-phosphonomethylthiolglycine octadecyl-N-phosphonomethylthiol-glycine), glycinamide ■ NN-dibutyl-iN-phosphonomethyD-glycinamide monosodium salt N- (phosphonomethyl) -glycine monoethylamine salt dichloroethyl-N- (phosphonomethyl) -glycinate trichlorobutyl-N- (phosphonomethyl) -glycinate

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Dibromohexyl N- (phosphonomethyl) glycinate Trifluoromethylphenyl N- (phosphonomethyl) glycinate Diehlophenyl-N- (phosphonomethyl) -glycinate Dibutylamine salt of N- (phosphonomethyl) -glycine Octadecylamine salt of N- (phosphonomethyl) -glycine Methoxyethylamine salt of N- (phosphonomethyl) -glycine Ethylenediamine salt of N- (phosphonomethyl) -glycine Pyrrolidine salt of N- (phosphonomethyl) -glycine Dipropanolamine salt of N- (phosphonomethyl) -glyein Chlorethylamine salt of N- (phosphonomethyl) -glycine ■ Phenoxyethylamine salt of N- (phosphonomethyl) -glycine N, N-diethylaminoethy1-N- (phosphonomethyl) glycinate.

Example 11

To demonstrate the phytotoxic activity of the invention Alligator herb (Alternanthera philoperorides) was combined with an aqueous compound against aquatic plant species Solution of N-phosphonomethylglycine in the proportion of 0.06 kg (0.125 pounds) sprayed per acre. The plants were kept under greenhouse conditions for four weeks. The behavior of the Plants were noted. At the end of the four week period, all of the plants had died. The control plants were normal after four weeks.

Example 12

The herbicidal activity after emergence (post-emergence herbicidal activity) is demonstrated as follows. The active ingredients are based on 14- to 21-day-old samples of different Plant species (as indicated) sprayed on. A solution of the active ingredient and a wetting agent is used as the rinsing liquid (35 parts of the butylamine salt of dodecylbenzenesulfonic acid and 65 parts of tall oil condensed with ethylene oxide, the molar ratio being Ethylene oxide to tall oil is 11: 1) in water or a mixture of an organic solvent and water on the plants in different sets of bowls in different

209839 / Ί201 " ¹⁸ ~

different ratios (kg per morning) of the active ingredient applied. The treated plants are transferred to a greenhouse and after about two weeks or about The effects are observed and noted for four weeks. The results obtained are shown in Table I.

The index of herbicidal activity after inoculation in Table I is defined as follows.

Plant Behavior Index

No damage 0

Minor damage 1 -

Moderate damage 2

Serious damage 3

Kill 4

The following plants were used.

A - soybean K - water pepper

B - sugar beet L - semolina

C - wheat M - fluff brisket

D - rice N- Panicum species

E - Sorghum 0 - Barn yard grass

P - burdock P - finger grass

G - Wild Buckwheat Q - Cypergrass'

H - winch R - field mercury '

I - Hemp S - Sudan grass ⁴ * '

J - White goosefoot or Melde T - Thistle

Established at the plant offshoots.

Table I.

Connection Ratio ABCDEFGHIJK.LMNOPQBST Week dung nis

I 1.81 4-2-4-44-4-434-

I 0.45 OI3I3212O2-I3433

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Table I continued

Connection Ratio ABCDEFGHIJKLMNOPQBST weeks dung nis

j. _f ui - - - - τ - JT -rrrT

II 0.45 3443432334-44

III 1.81 4-4-4-44

in 0.45 3444441 234433

IV 1.81 4-3-4-44

IV 0.45 3434443344-44

V 1.81 4-3-4-44

V 0.45 2444442234-34

VI 1.81 4_4 "4444

VI 0.45 3443443244-34

VII 1.81 3-I-3222

VIII 1.81 3-2-3433

IX 1.81 3-3-4433

X 1.81 3-3-4444

XI 1.81 4-3-4443

XII 1.81 4-3_4444

XIII 1.8I ⁺ * 4-2-3-31

XIV 1,8I ⁺ * O322IIO2 10

XV 4.54 ⁺ * 1-1-4--2

XVI 1.81 ^{+) 2-2-3232}

XVII 1.81 4-3-4-44

XVIII 1.81 - _; 3-1-4-33

XIX 1.81 3-2-3-33

XX 1.81 4-3-4-43

XXI 1.81 4-3-4-33

XXII 1.81 3-1-4.-43

XXIII 1.81 4-3-4-33

XXIV 1.81 4-2-4-34

XXV 1.81 4-2-4-44

XXVI 1.81 4-3-4-43

XXVII 1.81 4-2-4-43

- 4 - 4 4 4 _

4 4 4

443-

4 4 4

4444

4 4 4-

4 4 4

.4.4444

-3-1
-3-2
-3-2
-4-3
-4-3

- 4 - 2

-3-1

3 3 3-

- 4 - 1

- 2 - 1

- 4 - 4

- 3 - 2

- 2 - 2

-4-3
-3-4

- 2 - 2

- 4 - 4

-4-3

- 4 - 4

- 4 - 4
-4-3

232 4 4 3

4 3-4 4 4 3-4 4-4 213

4 2 0 0 2 2 4 4 4

3 3-

3 4-

4 4 4 4-4 14 3 4 4 4 4 4 4-4 4 4 4 4 4 4 2 1

2 2 2 2 2 4 2 2 2 2 2 2 2 2 2 2 2 2 2

209839/1201

-20-

Table I continued

Connection Ratio AB CDEFG HIJ KLHK OP QE S I Week ding

XXVIII

XXXII

XXXIII

XXXIV

1.81 1.81 1.81 1.81 1.81 1.81 1.81

if

k if if if if

3 - if

if - if

if - if

if - if

if - if

2 - if

2 - if

if 2

if if

if if

if if

if if

if if

if if

if
4th
if if if if

if if if 3

if if if if

if if _ if

4 if - if

if if - if

3 if if if

if if if if

2 2 2 2 2 2

Applied to three week old plants. All other experiments were carried out with two week old plants.

These readings were taken after 11 days.

The following table shows the compounds used:

number

link

II III IV

VI

VII

VIII

IX

XI

XII

XIII XIV XV

XVI

XVII

N-phosphonomethylglycine

Sodium N-phosphonomethyl glycinate

Disodium N-phosphonomethyl glycinate

Trisodium N-phosphonomethyl glycinate

N-phosphonomethylglycine monoethanolamine salt

N-phosphonomethylglycine monoanimonium salt

Monohydrate calcium salt of N-phosphonomethylglycine

Magnesium salt of N-phosphonomethylglycine Magnesium bis (N-phosphonomethyl glycinate) Potassium salt of N-phosphonomethylglycine. Dimethylamine salt of N-phosphonomethylglycine Copper bis (N-phosphononiethylglycinate) Dilithium salt of N-phosphonomethylglycine Zinc salt of N- (phosphonomethyl) -glycine N-phosphonomethylglycine amide methyl N- (phosphonomethyl) glycinate

-21-

number

link

XVIII XIX XX

XXI

XXII

XXIII XXIV XXV

XXVI

χχνίΐ

XXVIII

XXIX

XXX

XXXI

XXXII

XXXIII

XXXIV

n-Propyl-N- (phosphonomethyl) -glycinate n-Butyl-N- (phosphonomethyl) -glycinate n-Hexyl-N- (phosphonomethyl) -glycinate Cyclohexyl-N- (phosphonomethyl) -glyc inate Octyl N- (phosphonomethyl) glycinate Decyl-N- (phosphonomethyl) -glycinate dodecyl-N- (phosphonomethyl) -glycinate Chloroethyl-N- (phosphonomethyl) -glycinate

Mono- (methylamine) salt of N-phosphonomethylglycine

Mono- (diisopropylamine) salt of N-phosphonomethylglycine

Mono- (diethanolamine) salt of N-phosphomethylglycine

Mono- (triethylamine) salt of N-phosphonomethylglyein

Mono- (pyridine) salt of N-phosphonomethylglycine

Mono- (aniline) salt of N-phosphonomethylglycine

Bis (N-phosphonomethylglycine) hydrochloride hydrate

Mono- (isopropylamine) salt of N-phosphonomethylglycine

Mono- (n-butylamine) salt of N-phosphonomethylglyein

The agents according to the invention are for minimal rivet testicles extremely suitable for harvest crops. For example, in cases where it is desired, a lawn or other Way "planted area with wharves or, grain or the like without plowing or some other mechanical preparation of the seed bed are planted, the seeds for the crop in combination be sown in series with a previous or subsequent application of the agent according to the invention to to prevent the undesired growth of plants if the agent is applied before the crop emerges or emerges will.

-22-

209839/1201

The compositions according to the invention are also suitable for the renovation or conversion of lawns (ordinary lawn, alfalfa, willow and the like). For example, in cases where a lawn or parts of it has been overgrown by undesirable plant species, the plants in that area can be sprayed with the phytotoxic gown of the invention in order to control all growing plants. After about two to 2k hours, depending on the weather conditions, the desired species can be sown in the dying vegetation. If a seed bed is being made, about 2 to 3 weeks should elapse between treatment and making the seed bed to allow sufficient time for the agent to be assimilated by all parts of the undesired plants.

In an alternative method of lawn renovation, the area can be sown and immediately afterwards with one of the invention Means to be sprayed.

In either method, the seeds fall under the vegetation. At the When the sprayed plants wither and die, they act as a cover of leaves and as a moisture-retaining layer in which the seeds can germinate. This approach is particularly useful for renovating lawns or golf courses or Suitable for fairways because the herbicidal effect of the agents according to the invention is strong when they come into contact with the earth is diminished or completely eliminated »Thus, seeds that are in the earth can degenerate with no apparent effect Spraying the unwanted plants before the time the seeds actually germinate, germinate and grow.

The compositions of the invention provide a wide spectrum of weed control and are also more extreme Useful as a general herbicide as well as for controlling unwanted plants in orchards, tree gardens and various Crop fields. It was found, for example, that if one

• »23— 209839/1201

- 453 -

wanted plants sprayed with the smocks according to the invention, and thereby a substantial contact with the leaves of the trees prevents the unwanted plants from being controlled while the trees suffer no apparent damage. at such direct spraying may cause the sprayed agent to fall on the woody part of the fruit tree or other trees, without any apparent effects. Thus, the direct spray method is useful in crop fields such as plantations, for example of rubber, coffee, bananas, tea etc. and in orchards, such as citrus fruits, apples, peaches, pears, nuts and olives, suitable in vineyards and blackberry fields and in undersown crops for the control of undesirable plants «The It is also suitable for cotton, soybeans, sugar cane and the like.

The agents according to the invention are also used for weed control between the harvest times, for the renovation of used seed beds and the like.

When applying the agents according to the invention to the plants, which are to be checked, it has proven to be expedient that the plants have emerged from the earth, it is more desirable for the plant to be at least in the second stage of foliage for maximum effect.

It has been found that if the plants to be controlled have part of their growth above the ground or above the Have water and if the parts of the plants above or above the water with the herbicidal agents of the invention are brought into contact in suitable proportions, the herbicide is further transported in the plants and also causes those parts of the plant to die that lie beneath the earth or water.

209839/1201

With crops such as cotton, soybeans, sugar cane and the like, limited selectivity can be obtained if the spray stream of the compositions according to the invention is directed at a selected concentration onto the vegetation around the base of such plants and only minimal spray contact with the deciduous parts of such crops Permitted Directional spraying can be done with or without the use of a guard to prevent the spray stream from contacting the leaves of such crops.

The following is a non-exhaustive list of plant species which are controlled by the compositions of the invention can, in addition to the plants in Table I:

Kedicago Sativa Lolium multiflorum Hordeum murinum Alopecurus myosuroides Agrostis tenuis

Phaseolus vulgaris var. Humilies

Daucus carota var. Sativa Stellaria media Agrostemm'a githago Gossypium hirsutum Agropyron cristatum Rumex crispus Paspalum dilatatum Amsinckia intermedia Setaria faberii Setaria viridis Seeale cereale Lamium amplexicaule Datura stramonium Arachis Hypogaea Solanum tuberosum Cyperus rotundus

Poa Annua
Hordeum vulgar Galium aparine Bracharia platyphylla Plantago lanceolata Mollugo verticillata

Portulaca oleracea Zea mays

Spergula arvensis Saponaria vaccaria Cucumis safeivus Eriochloa gracilis Camelina microcarpa Linum usitatissimum Ambrosia trifida Lithospermum officinale Sisymbrium officinale Brassica juncea Avena sativa Pisum sativum Sida spinosa Polypogon monspeliensis

209839/1201

-25-

Eaphanus sativus Rottboellia exaltata Beta vulgaris Amaranthus retroflexus Cenchrus pauciflorus Cassia obtusifolia Zea mays var.Saccharate Lycopersicon esculentum Sorghum bicolor Avena fatua
Plantation · lanceolata Dactylis glomerata Solanum carolinense Pranseria tomentosa Festuca arundinaceae Agrostis spp Panicuin dichotomiflorum Pennisetum clandestinum Mikania cordata Imperata cyliridrica Scleria bancara Eleucine indica

Ambrosia artemisiifolia Brassica napus Oryza sativa Poa trivialis Rumex acetosella Andropogon saccharοides Fagopyrum tataricum Citrullus vulgaris Erassica kaber var "pinnatifida Erigeron canadensis Trifoliuin pretense Daucus carota Solarium elaegnifolium Poa pratensis Pestuca rubra Cynodon dactylon Cornmelina diffusa or cornmunis Paspalum spp Ottochloa nodosa Axonopu s c omp re s s u s Commellina nudiflora

The phytotoxisehen agents of the invention with the inclusion of concentrates which require dilution prior to application contain at least one active ingredient and an adjuvant in liquid or solid Porm _o The compositions are prepared by mixing the active ingredient with an adjuvant. Such auxiliaries are, for example, diluents, extenders, carriers and conditioning agents. In this way, agents are obtained in the form of finely divided granules, pellets, solutions, dispersions or emulsions. Thus, the active ingredient can be used with an auxiliary such as finely divided solids, liquids of organic origin, water, humectants, dispersants, emulsifiers or a mixture of these substances . For economic reasons and in the interest

-26-

209 839/1201

easy handling, water is used as the diluent, particularly preferred for the highly water-soluble glycine salts, such as the alkali metal salts and the amine and ammonium salts. These derivatives can be used to produce solutions that are up to 2.2? kg or more of active ingredient each contain 3 »8 liters.

The phytotoxic gowns of the invention, particularly those Liquid agents and the gowns in the form of soluble powders preferably contain as conditioning agents at least one wetting agent in sufficient quantity that a particular composition is readily dispersible in water or oil is made. The addition of a butcher to the mixtures increases the effectiveness considerably. Under the designation "Wetting agents" should be humidifying agents, dispersing agents, Suspending agents and emulsifiers are covered. Anionic, cationic and non-ionic gowns can be used will.

Preferred wetting agents are alkylbenzene and alkylnaphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, long-chain acid esters of sodium isothionate, esters of sodium sulf osuccinate, sulfated or sulfonated fatty acid esters, petroleum sulfonates, sulfonated vegetable oils, ditertiary acetylene glycols, Polyoxyethylene derivatives of alky! Phenols (in particular Isooctylphenol and Nonylpheiiol) and polyoxyethylene derivatives of monoesters of higher fatty acids or of hexitol anhydrides (e.g. sorbitol). Preferred dispersants are methyl cellulose, Polyvinyl alcohol, sodium lignosulfonate, polymeric alky naphthalene sulfonates, sodium naphthalene sulfonate, polymethylene bis-naphthalene sulfonate and sodium N-methyl-N (long chain) laurates.

V / water dispersible powder gowns can be produced which contain at least one active ingredient, an inert solid extender and one or more wetting and dispersing agents

-27- 209839/1201

contain funds. The inert solid extenders are usually of mineral origin such as the natural clays, diatomaceous earth, and synthetic minerals derived from silica and the like. Examples of such extenders are kaolinite, attapulgite clay and synthetic agnesiumsilicate. The water-dispersible powders according to the invention usually contain about 5 to about 95 parts by weight of active ingredient, about 0.25 to 25 parts by weight of wetting agent, et. About 0.25 bin 25 parts by weight of dispersant and 4.5 to about: a 94.5 parts by weight of an inert solid extender All parts are based on the weight of the total mixture Corrosion inhibitor and / or an antifoam agent can be replaced.

Aqueous suspensions can be prepared by adding aqueous Slurries of water-insoluble active ingredients mixed together in the presence of dispersants and ground will. In this way concentrated slurries of very finely divided particles are obtained. The received concentrated aqueous suspensions are characterized by their extremely small particle size, so that upon dilution and spraying a very even coverage is obtained.

Emulsifiable oils are usually solutions of active ingredients in V / ater immiscible or partially V / ater immiscible solvents together with a surface-active solvent Smock. Suitable solvents for the active ingredients of the invention include hydrocarbons and water immiscible ones Ethers, esters and ketones. The emulsifiable oil blends generally contain about 5 to 95 parts of active ingredient, about 1 to 50 parts of the surfactant and about 4 to 94 parts of solvent. All parts are based on total weight of the emulsifiable oil.

209839/1201

SAD ORIGINAL

Although the agents according to the invention also contain other additives such as fertilizers, phytotoxic agents and regulators for plant growth, pesticides and similar substances used as auxiliaries or in combination with the above Aids can be used, it is preferred to use the agents according to the invention for Achieving maximum effect alone or alternating with other phytotoxic agents, fertilizers and the like to use. For example, the field with an agent according to the invention can be applied either before or after treatment sprayed with fertilizers, other phytotoxic agents, and the like. The agents according to the invention can also be mixed with other materials, e.g. fertilizers, other phytotoxic substances and the like and can be used in a single application. Chemicals in combination with the active ingredients of the invention are suitable either at the same time or alternately, are e.g. triazines, ureas, carbamates, acetamides, acetanilides, uracile, acetic acids, phenols, thiocarbamates, triazoles, Benzoic acids, nitriles and the like.

Examples of this are the following compounds:

3-Amino-2,5-dichlorobenzoic acid 3-Amino-1,2, ^ - triazole

2-methoxy - ^ - ethylamino-6-isopropylamino-s-triazine 2-chloro - ^ - ethylamino-6-isopropylamino-s-triazine 2-chloro-N, N-diallylacetamide 2-chloroallyldiethyldithiocarbamate NM ^ -Chlorophenoxy) -phenyl-N, N-dimethylurea 1,1 '-Dimethyl -4, * f' -bipyridinium dichloride Isopropyl m- (3-chlorophenyl) carbamate 2,2-dichloropropionic acid

S-2,3-dichloroallyl-N, N-diisopropylthiolcarbamate 2-methoxy-3,6-dichlorobenzoic acid 2,6-dichlorobenzonitrile

-29- 209839/1201

N, N ~ dimethyl-2,2-diphenylacetamide 6,7-dihydrodipyrido- (1,2-a: 2 ·, 1 · -c) -pyrazidiinium salt 3_ (3, ^ - dichlorophenyl) -1, 1-dimethylurea ty, 6 ~ Dinitro-o-sec-butylphenol
2-ethyl-ty, 6-dinitrophenol
Ethyl N, N-dipropyl thiol carbamate
2,3,6-trichlorophenylacetic acid
5-bromo-3 ~ isopropyl-6-methyluracil 3- (3 _t 4-dichlorophenyl) -l ~ methoxy-l-methyl-urea! ^2-methyl-i J-chlorophenoxy acetic acid. 3- (p-Chlorophenyl) -1, 3-cLimethylurea 1-Butyl-3- (3,4-cLichlorophenyl) 4-methylurea NI-naphthylphthalic acid
1,1'-Dimethyl- ^, 4'-bipyridiniura salt 2-chloro-4,6-bis- (isopropylamino) -s-triazine 2-chloro- ^, 6-bis- (ethylamino) -s-triazine 2,4 -Dichlorophenyl- ⁱ l-nitrophenyl ether oC, (X ,, ds -Trifluoro-2,6-dinitro-N, N-dipropyl-p-toluidine S-propyl-dipropylthiol carbamate
2, * J — dichlorophenoxyacetic acid
N-isopropyl-2-chloroacetaniliri

2 ', 6 ^l -diethyl-N-methoxymethyl ~ 2-chloroacetanilide monosodium acid methane arsenate disodium methane arsenate
N- (1,1-Dimethylpropynyl) -3,5-dichlorobenzene amide

Fertilizers that are suitable in combination with the active ingredients are e.g. ammonium nitrate, urea, potash and Supe rpho sphat.

In proceeding according to the invention, effective amounts of the glycines are applied to aerial parts of the plants. the Application of liquid and in particular of solid herbicidal mixtures to above-ground parts of the plants can after happen with conventional methods, e.g. under use of pressure atomizers, boom and hand sprayers and spray

-30- 209839/1201

Atomize «, the means can also be used by plug generators as dust or applied as a spray stream because they are effective at low dosages. The use of herbicidal agents on aquatic plants is usually done by applying the agent to the aquatic plants in the area where control is desired will be sprayed on.

The application of an effective range of the invention Connections to the plant is essential and critical to the practice of the invention. The exact kenge of the used Active ingredients depend on the behavior of the plant as well as on other factors such as the plant species and the stage of development as well as the amount of rain and the specific glycine. When treating foliage to control vegetative growth the active ingredients in amounts of about 0.005 kg to about Applied 9.07 kg (0.01 to about 20 pounds) per acre. In the control of aquatic plants, the active ingredients are used in amounts of about 0.01 ppm to about 1000 ppm, based on the aqueous Medium, applied. An effective amount for phytotoxic or herbicidal control is that amount for one Total or selective control is required, i.e. a phytotoxic or herbicidal amount. In individual cases, the required Amount can easily be determined by a few preliminary experiments.

The agents according to the invention are also suitable as harvesting aids for many useful plants. For example, the useful plants be sprayed with the agents according to the invention in order to reduce the volume of the undesired material and the harvesting of crops to facilitate. Such useful plants are z “3. Peanut plants, soybeans and root plants such as potato, sugar beet, beetroot and the like.

-31-

209839/1201

IAD ORIGINAL

Claims (5)

Claims 1. / Compounds of the general formula 0 H 0 _R 1 R - C-CH ₀ -N-CH ₀ P 12th wherein R, R and R _1, which can be the same or different, mean: Halogen; -OH; -SH; -NR R, where R and R, which can be identical or different, are hydrogen, alkyl and hydroxyalkyl, each with 1 to 4 carbon atoms, alkenyl with 2 to 4 carbon atoms 4 5
and where R and R together with the nitrogen atom can form a heterocyclic ring: -OR ^ and -SR, where R is monovalent hydrocarbon groups, monovalent hydrocarbonoxy hydrocarbon groups respectively having 1 to 18 carbon atoms, halogenated monovalent hydrocarbon groups, halogenated monovalent hydrocarbonoxy hydrocarbon groups each having 1 to 18 carbon atoms and 1 to 3 halogen atoms and / or the groups ⁿ »where η is 1 to 4 and R and R ^ the above R ⁹
have given meanings, with the proviso that no more than two of the groups R, R and R are the radicals -NR R ³ , ■ χ -ζ.
-OR or -SR ^ are and -OR, where R is a salt-forming cation of alkali metals, alkaline earth metals, copper, zinc, manganese, nickel, ammonium and / or organic ammonium, with the proviso that, - 32 209839/1201 when the organic group is an aryl group, the ammonium salt is a primary amine salt or a mixture of such salts, 1 ? provided that when a substituent of R, R and R 1 is 2 halogen, the other substituents of R, R and R are not -OR and with the further proviso that not more than two the substituents R, R and R are -OR when R is ammonium or organic ammonium as well as the salts of strong acids of such compounds, 1 7
in which R, R and R are -OH groups, the strong acids having a pK value of 2.5 or less, with the proviso that if these compounds are not a salt of a strong 1 is 2 acid, - then no more than 2 groups R, R and R for the -OH remainder. 2. Compounds according to claim 1, characterized in that they contain the mono- (methylamine) salt of N-phosphonomethylglycine, the mono- (isopropylamine) salt of N-phosphonomethylglycine, the mono- (butylamine) salt of N-phosphonomethylglycine, the monoethanolamine salt of N ~ phosphonomethylglycine, the monodimethylamine salt of N-phosphonomethylglycine, the monoammonium salt of N-phosphonomethylglycine, the monosodium salt of N-phosphonomethylglycine, the disodium salt of N-phosphonomethylglycine, the trisodium salt of N-phosphonomethylglycine, Methyl-N-phosphonomethylglycinate, ethyl-N-phosphonomethylglycinate, Propyl-N-phosphonomethylglycinate or chloroethyl-N-phosphonomethylglycinate. 3. Phytotoxic agent, characterized in that that, in addition to an auxiliary, there is an effective amount of at least one compound of the general formula 0 H 0 _D 1 l \ ι H / ^R RC-CH ₀ -N-CH ₅ P 2 2 \ ₂ contains, in which R, R and R ² , which can be the same or different, are: -. 33 209839/1201 Halogen; -OH; -SH; NR R, where R and R ^, which are the same or different can be hydrogen, alkyl or hydroxyalkyl with 1 to 4 carbon atoms, alkenyl with 2 to 4 carbon atoms, and 4 5 where R and R ^ together with the nitrogen atom form a heterocyclic Can form ring; '6 ⁷ J 3 -OR and -SR, where R is monovalent hydrocarbon groups, monovalent hydrocarbonoxy hydrocarbon groups each having 1 to 18 carbon atoms, halogenated monovalent hydrocarbon groups, halogenated monovalent hydrocarbonoxy hydrocarbon groups each having 1 to 18 carbon atoms and 1 to 3 halogen atoms and / or the groups / R ⁴ _{-CJ 0} -N, where n is 1 to 4 and R and R ^ the above η 2n \ » R ⁵ Have given meanings, with the proviso that 1 ? 4 5 no more than two of the groups R, R and R the radicals -NR R, -OR * or-SR ^ are and -OR, where R is a salt-forming cation of alkali metals, alkaline earth metals, copper, zinc, manganese, nickel, ammonium, and / or organic ammonium, provided that when the organic group is an aryl group, the ammonium salt is a primary amine salt or a mixture of such salts, with the proviso that when a substituent of R, R 2 and R is halogen, the other substituents of R, R and R are not -OR and with the further proviso that no more as two of the substituents R, R and R stand for -OR, when R is ammonium or organic ammonium, as well as the salts of strong acids of such compounds, 1 p
where R, R and R are -OH groups, the strong acids having a pK value of 2.5 or less. 4. Means according to claim 3, characterized in that it is the monodimethylamine salt of N-phosphonomethylglycine as the active ingredient, the monoethanolamine salt of N-phosphonomethylglycine, the monoammonium salt of N-phosphonomethylgly - 34 2Ü9839 / 1201 one, the mono- (butylamine) salt of N-phosphonomethylglycine, the mono- (isopropylamine) salt of N-phosphonomethylglycine, the mono- (methylamine) salt of N-phosphonomethylglycine, the monosodium salt of N-phosphonomethylglycine, the disodium salt of N-phosphonomethylglycine, the trisodium salt of N-phosphonomethylglycine , N-phosphonomethylglycine, methyl-N-phosphonomethylglycinate, Ethyl-N-phosphonomethylglycinate, and / or Contains chloroethyl-N-phosphonomethylglycinate. 5. A method for controlling plants, characterized in that the plant is a phytotoxic Amount of a compound of the general formula 0 H 0 "1 Ii I Il ^R RC-CH ₀ -N-CH ₀ P 1 2
exposing, where R, R and R, which can be the same or different, mean: Halogen; -OH; -SH; NR ¹ S? wherein R and R, which can be the same or different, are hydrogen, alkyl and hydroxyalkyl each having 1 to carbon atoms, alkenyl having 2 to k carbon atoms and where R and R together with the nitrogen atom can form a heterocyclic ring; r) τ r> -OR ^ and -SR, where R ^ monovalent hydrocarbon groups, monovalent hydrocarbonoxy hydrocarbon groups each having 1 to 18 carbon atoms, halogenated monovalent Hydrocarbon groups, halogenated monovalent hydrocarbonoxy hydrocarbon groups each having 1 to 18 carbon atoms and 1 to 3 halogen atoms and / or the groups -CH ₀ -NC t, where η is 1 to H- and R and R ^ are as above η 2n \ r5 Have given meanings, with the proviso that no more than two of the groups R, R "and R for -NRr, -OR ' or -SR ^ stand and 209839/1201 -OR, where R is a salt-forming cation of alkali metals, Alkaline earth metals, copper, zinc, manganese, nickel, ammonium and / or organic ammonium, with the proviso that, when the organic group is an aryl group, the ammonium salt is a primary amine salt or a mixture of such salts, 1 ? provided that when a substituent of R, R and R 1 2 is halogen, the other substituents of R, R and R are not -OR are and with the other proviso that no more than two of the substituents R, R and R stand for --0R, v / when R Is ammonium or organic ammonium as well as the salts of strong acids of such compounds 1 2 genes where R, R and R are -OH groups, the strong ones Acids have a pK value of 2.5 or less. 209839/1201 ORIGINAL INSPECTED